Structure and bonding Structures of the elements There is a trend from non-metal to metal as you go down the Group

which is clearly seen in the structures of the elements. Carbon at the top of the Group has giant covalent structures in its two most familiar allotropes - diamond and graphite.
Allotropes: Two or more forms of the same element in the same physical state. The structures of diamond and graphite are explored in more detail on a page about giant covalent structures in another part of this site. It would probably be worth your while to read this page before you go any further. Use the BACK button on your browser to return quickly to this page.

Diamond has a three-dimensional structure of carbon atoms each joined covalently to 4 other atoms. The diagram shows a small part of that structure.

Exactly this same structure is found in silicon and germanium and in one of the allotropes of tin - "grey tin" or "alpha-tin".

The common allotrope of tin ("white tin" or "beta-tin") is metallic and has its atoms held together by metallic bonds. The structure is a distorted close-packed arrangement. In close-packing, each atom is surrounded by 12 near-neighbours. By the time you get to lead, the atoms are arranged in a straightforward 12-co-ordinated metallic structure.
Note: If you aren't sure about metallic bonding or metallic structures, you should follow these links before you go any further. The first link will actually lead you to the second one if you want to explore both of these topics. Use the BACK button on your browser to return to this page.

So the bonding in the elements at the top of the Group is giant covalent. At tin, there are two forms, one of which is giant covalent, and one of which is metallic. At lead, the bonding is entirely metallic.

Physical properties of the elements CIE expect you to be able to describe and explain the variation in melting point and electrical conductivity in terms of the changes in the structure and bonding of the elements as you go down Group 4. Trends in melting point The following bar chart shows the trends in both melting and boiling points. Although they aren't mentioned by CIE, boiling points actually give a better indication of interatomic forces than melting points do. The bonds aren't fully broken until you boil the substance.

You will see that the trend is for melting and boiling points to fall as you go down the group.
Note: The low value for tin's melting point compared with lead is presumably due to tin forming a distorted 12-co-ordinated structure rather than a pure one. The tin values in the chart refer to metallic white tin.

Comparing carbon, silicon and germanium (all of which have giant covalent structures), the melting points fall because the atoms are getting bigger. That means that the bonding pairs of electrons are further from the nuclei, and so the bonds are weaker. It would be dangerous to make a simple comparison between these first three elements and tin and lead, because the bonding is different - metallic rather than covalent. Obviously, though, these metallic bonds are weaker than the covalent bonds in the first three elements because the melting and boiling points are lower. The boiling pint of lead is lower than that of tin as you would expect. The atoms are bigger, and a longer bond is a weaker bond.

Electrical conductivity You have to look at the elements on a case-by-case basis. Carbon Carbon as diamond doesn't conduct electricity. In diamond the

electrons are all tightly bound and not free to move. However, carbon as graphite does conduct. The reason (not wanted by CIE) is that in the graphite structure each atom donates one electron to a delocalised system of electrons which takes in the whole of its layer (rather like an extended benzene). These electrons are free to move around, and so graphite conducts electricity - but this is a special case. Silicon and germanium Silicon and germanium are semiconductors. The theory of semiconductors is beyond A level chemistry, but if you are interested in a brief introduction, then you could read the big green box about half-way down the page about the trend from non-metal to metal in Group 4. For CIE A level chemistry purposes, you can pick out whether a substance is a normal conductor or a semiconductor by the effect of heat on the resistance of the material. In metals, the conductivity falls if you increase the temperature. In semiconductors, the conductivity increases at higher temperatures. Tin and lead White tin (normal metallic tin) and lead are good metallic conductors of electricity.

The only clear-cut cases here are diamond and the two metals. In diamond, the covalent bonding stops the electrons moving. In tin and lead, you have delocalised electrons. For silicon and germanium, you can say that they aren't normal conductors because they don't have any delocalised electrons, due to the covalent bonding. But without going into the theory of semiconductors, for A level chemistry, it is impossible to explain why they act as semiconductors. THE TREND FROM NON-METAL TO METAL IN THE GROUP 4 ELEMENTS

This page explores the trend from non-metallic to metallic

behaviour in the Group 4 elements - carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). It describes how this trend is shown in the structures and physical properties of the elements, and finally makes a not entirely successful attempt to explain the trend.

Structures and Physical Properties Structures of the elements The trend from non-metal to metal as you go down the Group is clearly seen in the structures of the elements themselves. Carbon at the top of the Group has giant covalent structures in its two most familiar allotropes - diamond and graphite.
Allotropes: Two or more forms of the same element in the same physical state. The structures of diamond and graphite are explored in more detail on a page about giant covalent structures in another part of this site. It would probably be worth your while to read this page before you go any further. Use the BACK button on your browser to return quickly to this page.

Diamond has a three-dimensional structure of carbon atoms each joined covalently to 4 other atoms. The diagram shows a small part of that structure.

Exactly this same structure is found in silicon and germanium and in one of the allotropes of tin - "grey tin" or "alpha-tin". The common allotrope of tin ("white tin" or "beta-tin") is metallic and has its atoms held together by metallic bonds. The structure is a distorted close-packed arrangement. In close-packing, each atom is surrounded by 12 near-neighbours. By the time you get to lead, the atoms are arranged in a straightforward 12-co-ordinated metallic structure.
Note: If you aren't sure about metallic bonding or metallic structures, you should follow these links before you go any further. The first link will actually lead you to the second one if you want to explore both of these topics. Use the BACK button on your browser to return to this page.

There is therefore a clear trend from the typical covalency found in non-metals to the metallic bonding in metals, with the change-over obvious in the two entirely different structures found in tin.

Physical properties of the elements

Melting points and boiling points If you look at the trends in melting and boiling points as you go down Group 4, it is very difficult to make any sensible comments about the shift from covalent to metallic bonding. The trends reflect the increasing weakness of the covalent or metallic bonds as the atoms get bigger and the bonds get longer.

The low value for tin's melting point compared with lead is presumably due to tin forming a distorted 12co-ordinated structure rather than a pure one. The tin values in the chart refer to metallic white tin.
Note: The data in this chart comes from the University of Sheffield's excellent Webelements site. There is an awful lot of variability in the data depending on where you get it from. I have to admit to choosing this set because it shows simple, largely unbroken patterns!

Brittleness There is a much clearer non-metal / metal difference shown if you look at the brittleness of the elements. Carbon as diamond is, of course, very hard reflecting the strength of the covalent bonds. However, if you hit it with a hammer, it shatters. Once you apply enough energy to break the existing

carbon-carbon bonds, that's it! Silicon, germanium and grey tin (all with the same structure as diamond) are also brittle solids. However, white tin and lead have metallic structures. The atoms can roll over each other without any permanent disruption of the metallic bonds - leading to typical metallic properties like being malleable and ductile. Lead in particular is a fairly soft metal.

Electrical conductivity Carbon as diamond doesn't conduct electricity. In diamond the electrons are all tightly bound and not free to move.
Note: In graphite, each atom donates one electron to a delocalised system of electrons which takes in the whole of its layer. These electrons are free to move around, and so graphite conducts electricity but this is a special case. If you are interested, the bonding in graphite is like a vastly extended version of the bonding in benzene. 2 Each carbon atom undergoes sp hybridisation, and then the unhybridised p orbitals on each carbon atom overlap sideways to give a massive pi system above and below the plane of the sheet of atoms.

Unlike diamond (which doesn't conduct electricity), silicon, germanium and grey tin are semiconductors.
Semiconductors: The theory of semiconductors lies outside A level chemistry, but briefly . . . When lots of atoms come together to

make a giant structure, their atomic orbitals merge to produce a huge number of molecular orbitals, which arrange themselves in bands of increasing energy. One of these is often described as a valence band. The molecular orbitals in this band hold the electrons which make up the normal covalent (or metallic) bonding. The other band is called the conductance band. This usually has a higher energy than the valence band, and in something like diamond or silicon at absolute zero, the conductance band is empty of electrons. However, as electrons gain thermal energy as the temperature increases, some electrons may jump from the valence band into the conductance band - especially if the gap between the two is small. Once they are in the conductance band, they are delocalised from their original atoms and are free to move and conduct electricity. In diamond, the energy gap between the valence band and conductance band is too high for this to happen. In silicon, the band gap is small enough for electrons to jump, and so silicon is a semiconductor. If you are interested in this, you might like to try a Google search on silicon semiconductors band theory (or similar).

White tin and lead are normal metallic conductors of electricity. There is therefore a clear trend from the typically nonmetallic conductivity behaviour of carbon as diamond, and the typically metallic behaviour of white tin and lead.

Trying to explain the trends

The main characteristic of metals is that they form positive ions. What we need to do is to look at the factors which increase the likelihood of positive ions being formed as you go down Group 4. Electronegativity Electronegativity is a measure of the tendency of an atom to attract a bonding pair of electrons. It is usually measured on the Pauling scale, where the most electronegative element (fluorine) is given an electronegativity of 4. The lower the electronegativity of an atom, the less strongly the atom attracts a bonding pair of electrons. That means that this atom will tend to lose the electron pair towards whatever else it is attached to. The atom we are interested in will therefore tend to carry either a partial positive charge or form a positive ion. Metallic behaviour is usually associated with a low electronegativity.
Note: If you aren't sure about electronegativity you really ought to read about it before you go any further. Use the BACK button on your browser to return quickly to this page.

So what happens to electronegativity in Group 4? Does it decrease as you go down the Group, suggesting a trend towards metallic behaviour?

Well! It certainly falls from carbon to silicon, but from there on it is a complete mess! There therefore seems to be no relationship between the non-metal to metal trend and the electronegativity values. Assuming the electronegativity values are correct, I am completely at a loss to understand this!
Note: The data in this chart again comes from the University of Sheffield's Webelements site. Again, there is an awful lot of variability in the data depending on where you get it from. But in no case that I have found is there any trend to lower electronegativities as you go down the Group. Older data sources give a fall from carbon (2.5) to silicon (1.8), but then give all the other elements in the Group the same value (all 1.8). If anyone reading this has a simple explanation for the lack of correlation between the trend to metallic behaviour and the electronegativity values, could you please contact me via the address on the about this site page.

Ionisation energies If you are thinking about the formation of positive ions, the obvious place to start looking is how

ionisation energies change as you go down Group 4. Ionisation energies are defined as the energy needed to carry out each of the following changes. They are quoted in kJ mol-1. First ionisation energy:

Second ionisation energy:

. . . and so on.
Note: If you aren't sure about ionisation energies it would pay you to follow this link before you go any further. Use the BACK button on your browser to return quickly to this page.

None of the Group 4 elements form 1+ ions, so looking at the first ionisation energy alone isn't very helpful. Some of the elements do, however, form 2+ and (to some extent) 4+ ions. The first chart shows how the total ionisation energy needed to form the 2+ ions varies as you go down the Group. The values are all in kJ mol-1.

You can see that the ionisation energies tend to fall

as you go down the Group - although there is a slight increase at lead. The main trend is because:

The atoms are getting bigger because of the extra layers of electrons. The further the outer electrons are from the nucleus, the less they are attracted - and so the easier they are to remove. The outer electrons are screened from the full effect of the nucleus by the increasing number of inner electrons. These two effects outweigh the effect of the increasing nuclear charge.

Note: The reason for the oddity at lead is discussed in some more detail on a page about the oxidation states shown by elements in Group 4. It isn't particularly important to the present discussion.

If you look at the amount of ionisation energy needed to form 4+ ions, the pattern is similar, but not entirely clear cut. Again, the values are all in kJ mol-1.

Note: The increase in total ionisation energy at lead is even more obvious in the case of the possible formation of 4+ ions. This is important when it comes to looking at the preferred oxidation states of lead.

What is clear looking at these two charts is that you have to put in large amounts of ionisation energy to form 2+ ions, and huge amounts to form 4+ ions. However, in each case there is a fall in ionisation energy as you go down the Group which makes it more likely that tin and lead could form positive ions however, there is no indication from these figures that they are likely to form positive ions. The ionisation energies of carbon at the top of the Group are so huge that there is no possibility of it forming simple positive ions. Shapes and bonding

These all have the formula XCl4. They are all simple covalent molecules with a typical tetrahedral shape. All of them are liquids at room temperature. (Although even at room temperature, lead(IV) chloride will tend to decompose to give solid lead(II) chloride and chlorine gas.) CCl4 is typical:

Remember that simple lines show bonds in the plane of the paper (or screen), dotted lines show bonds going back into the paper, and wedges show bonds coming out towards you.

Volatility The more volatile a substance is, the lower its boiling point. The boiling points of these compounds are: B Pt (C) CCl4 SiCl4 GeCl4 SnCl4 PbCl4 76 57 87 114 decomposes at 105
Note: Several sources quote 105 C as the boiling point of PbCl4 - it isn't. It decomposes explosively at this temperature. That isn't the

same as boiling!

You can see that, apart from CCl4, the boiling points increase as you go down the Group. This is because of increasing van der Waals dispersion forces as the molecules get bigger. Bigger molecules have more electrons which can be polarised, and more space to polarise them over. So volatility decreases as you go down the Group.
Note: If you aren't sure about van der Waals dispersion forces, you should revise it by following this link before you go any further. Use the BACK button on your browser to return to this page.

In the teacher support material, CIE mention CCl4 as an oddity, but don't suggest any explanation for it. I have no idea what the explanation is, and haven't been able to find one either. There are several sites on the web where this question is raised, but none that I have found come up with a good answer. In fact, many of the answers are rubbish! Don't worry about this. Carbon tetrachloride (tetrachloromethane) Carbon tetrachloride has no reaction with water. If you add it to water, it simply forms a separate layer underneath the layer of water. It doesn't react on heating either.

Silicon, germanium and tin tetrachlorides These are also called silicon(IV) chloride, germanium(IV) chloride and tin(IV) chloride. Silicon tetrachloride reacts violently with water to give white solid silicon dioxide and steamy fumes of HCl.

Liquid SiCl4 fumes in moist air for this reason - it is reacting with water vapour in the air.

The germanium and tin compounds behave similarly. The CIE teacher support material says that hydrolysis happens increasingly readily as you go down this part of the Group, but they are all rapid reactions.

Lead(IV) chloride The CIE teacher support material doesn't mention this. The reaction is complicated by the fact that all of these reactions give off a lot of heat. In the case of lead(IV) chloride, the heat is enough to decompose the lead(IV) chloride into lead(II) chloride and chlorine. Any unchanged lead(IV) chloride would behave exactly like the silicon tetrachloride, producing solid lead(IV) oxide and HCl. But you would also get a precipitate of lead(II) chloride formed and chlorine gas. I wouldn't bother to spend much time learning this. I suspect that if it did come up, there would be enough information in the question to help you through it.

The explanations We need to explain two things - why the reactivity of the others increases down the Group, and why the CCl4 behaves completely differently.

Why does the reactivity increase as you go down the Group? As the Group 4 elements gets bigger, the bonds between them and the chlorine atoms get longer. Longer bonds are weaker and more easily broken. During the reactions, you have to break element-chlorine bonds and replace them by element-oxygen bonds. If the bonds to the chlorines are weaker, that will happen more easily.

Why doesn't CCl4 react with water? CCl4, of course, has the strongest bonds to the chlorines, but that isn't the main problem. Suppose a water molecule is going to react with the carbon tetrachloride. The reaction would have to start by the water molecule's oxygen attaching itself to the carbon atom via the oxygen's lone pair. A chlorine atom would get pushed off the carbon in the process.

There are two problems with this. First, the chlorines are so bulky and the carbon atom so small, that the oxygen can't easily get at the carbon atom.

. . . and even if it did, there will be a stage where there is considerable cluttering around that carbon atom before the chlorine atom breaks away completely. There is going to be a lot of repulsion between the various lone pairs on all the atoms surrounding the carbon.

That cluttering is going to make this half-way stage (properly called a "transition state") very unstable. A very unstable transition state means a very high activation energy for the reaction. The other problem is that there isn't a convenient empty orbital on the carbon that the oxygen lone pair can attach to. If it could attach before the chlorine starts to break away, that would be an advantage. Forming a bond releases energy, and that energy would therefore be readily available for breaking a carbon-chlorine bond. But in the case of a carbon atom, that isn't possible.

The situation with silicon (and the other) tetrachlorides is different. The silicon atom is bigger, and so there is more room around it for the water molecule to attack, and the transition state will be less cluttered. But silicon has the additional advantage that there are empty 3d orbitals available to accept a lone pair from the water molecule. Carbon doesn't have 2d orbitals because there are no such things. There are no empty 2-level orbitals available in the carbon case.

This means that the oxygen can bond to the silicon before the need to break a siliconchlorine bond. This makes the whole process energetically easier. The activation energy for the reaction will be significantly less. The oxides The elements form two ranges of oxides - monoxides and dioxides. That is because the elements have two possible oxidation states, +2 and +4. Monoxides include carbon monoxide, CO, tin(II) oxide, SnO, and lead(II) oxide, PbO. Dioxides include CO2, SiO2, SnO2 and PbO2. The two non-metal oxides would normally be called carbon dioxide and silicon dioxide. The metal oxides would normally be called tin(IV) oxide and lead(IV) oxide. But you may find the names used fairly interchangeably, so that lead(IV) oxide is often called lead dioxide, for example. Lead also has another oxide with the formula Pb3O4, called trilead tetroxide. This is a bright red solid known popularly as "red lead". Pb3O4 behaves chemically as if it were a mixture of PbO and PbO2 in the ratio 2PbO.PbO2. You will come across this again later on this page.

Bonding in the oxides In the non-metallic elements from carbon to germanium, the oxides are covalent. For CIE purposes, you can think of the metal oxides (of tin and lead) as being ionic. The CIE teacher support material says that SnO2 and PbO2 are most easily described as ionic, but with a degree of covalency - and so that is what you need to learn. It is worth looking separately at a few of the oxides in more detail.

The oxides of carbon The fact that the two oxides of carbon are gases must mean that they are simple molecular substances.

Carbon monoxide can be thought of as having two ordinary covalent bonds between the carbon and the oxygen plus a coordinate bond using a lone pair on the oxygen atom.

In carbon dioxide, carbon forms simple molecules with oxygen because of the possibility of carbon-oxygen double bonds.

None of the other elements in Group 4 form double bonds with oxygen, and so that forces completely different structures on them.

Silicon and germanium dioxides Neither of these elements form double bonds with oxygen.
Mainly for interest: Silicon atoms are bigger than carbon atoms. That means that siliconoxygen bonds will be longer than carbon-oxygen bonds. To make a double bond, you have to have sideways overlap between p orbitals on adjacent atoms. With the longer siliconoxygen bonds, the p orbitals on the silicon and the oxygen aren't quite close enough together to allow enough sideways overlap to give a stable pi bond. So, silicon bonds with oxygen in such a way that only single bonds are formed. Similarly with germanium.

There are various different structures for silicon dioxide. The easiest to remember and draw is:

This is based on a diamond structure with each of the silicon atoms being bridged to its other four neighbours via an oxygen atom. This means that silicon dioxide is a giant covalent structure. The strong bonds in three dimensions make it a hard, high melting point solid. Exactly the same is true of germanium dioxide.

The tin and lead oxides If you think of these as ionic, then SnO and PbO will have giant ionic lattices consisting of Sn2+ or Pb2+ ions and oxide ions. SnO2 and PbO2 will have giant ionic lattices consisting of Sn4+ or Pb4+ ions and oxide ions.

The acid-base behaviour of the oxides Before we get bogged down in detail, here is a summary of the important points.

The oxides of the elements at the top of Group 4 are slightly acidic, but the acidity of the oxides falls as you go down the Group. Towards the bottom of the Group, the oxides have basic properties as well as acidic ones - in other words, they are amphoteric. The trend is therefore from acidic oxides at the top of the Group towards amphoteric ones at the bottom. Carbon and silicon dioxides are acidic. (There is a question mark over carbon monoxide - see later.) The germanium, tin and lead oxides are all amphoteric.

The dioxides of germanium, tin and lead tend to have more acidic character than the monoxides.

The oxides of carbon Carbon monoxide is only slightly soluble in water and doesn't react with it. It is normally counted as a neutral oxide. CIE describe it as neutral in their teacher support material - and so that is what you must learn.
Note: Carbon monoxide does in fact react with hot concentrated sodium hydroxide solution to produce sodium methanoate. The fact that the carbon monoxide reacts with the basic hydroxide ion shows that it must be acidic.

Carbon dioxide is weakly acidic. With water Carbon dioxide reacts with water to a slight extent to produce hydrogen ions (strictly, hydroxonium ions) and hydrogencarbonate ions. Overall, this reaction is:

The solution of carbon dioxide in water is sometimes known as carbonic acid, but in fact only about 0.1% of the carbon dioxide has actually reacted. The position of equilibrium is well to the left-hand side. With bases Carbon dioxide reacts with sodium hydroxide solution in the cold to give either sodium carbonate or sodium hydrogencarbonate solution - depending on the reacting proportions.

Silicon dioxide Silicon dioxide doesn't react with water, because of the difficulty of breaking up the giant covalent structure. Silicon dioxide does react with sodium hydroxide solution, but only if it is hot and concentrated. Sodium silicate solution is formed.

Silicon dioxide is weakly acidic.

Germanium, tin and lead oxides The monoxides All of these oxides are amphoteric - they show both basic and acidic properties. The basic nature of the oxides is shown by their reaction with acids to form salts. For example, they all react with hydrochloric acid. This can be summarised as:

For example, with tin(II) oxide, you get tin(II) chloride and water.

The acidic nature of the oxides is shown by their reaction with bases like sodium hydroxide solution. In general terms:

For example, with tin(II) oxide, you get sodium stannate(II) solution

and water. The stannate name is given to ions where tin is a part of the negative ion. The (II), of course, shows the tin in the +2 oxidation state.

Note: There are various versions of the formulae for compounds like sodium stannate(II). This is the simplest one, and is acceptable to CIE.

The dioxides These dioxides are again amphoteric - showing both basic and acidic properties. The basic nature of the dioxides is shown by their reaction with concentrated hydrochloric acid to give compounds of the type XCl4:

Note: The XCl4 actually goes on to react with excess chloride ions in the hydrochloric acid to 2give complexes such as XCl6 , but this isn't required by CIE.

In the case of lead(IV) oxide, the reaction has to be done with icecold hydrochloric acid. If the reaction is done any warmer, the lead(IV) chloride decomposes to give lead(II) chloride and chlorine gas. This is an effect of the preferred oxidation state of lead being +2 rather than +4. The reaction with hydrochloric acid isn't typical of lead(IV) oxide, which doesn't react with most acids.

The acidic nature of the dioxides is shown by their reaction with hot concentrated sodium hydroxide solution or molten sodium hydroxide. In general terms:

For example, with tin(IV) oxide, you get sodium stannate(IV) and

water.

Note: As in the case of the similar compound formed with tin(II) oxide, there are various formulae for the product in this reaction. This is the simplest, and is acceptable to CIE.

The special case of Pb3O4 You may remember that Pb3O4 can be thought of chemically as a mixture of 2PbO.PbO2. If you react this with an acid, then the two oxides which can be thought of as making up the Pb3O4 behave independently. For example, the PbO will react with nitric acid to give lead(II) nitrate solution and water:

However, the lead(IV) oxide doesn't react with nitric acid. Thinking of Pb3O4 as 2PbO.PbO2, the PbO would react with the nitric acid, and the PbO2 would be left over.

Care! This equation came up in a CIE question. The examiner's report said that many candidates forgot to multiply the lead(II) oxide part of the equation by two. That would be an annoying mistake to make, because you have already done the hard part by working out or remembering that it can be thought of as 2PbO.PbO2.

The thermal stability of the oxides

This is about the way the oxides are affected by heating. The monoxides CO, SiO and GeO Apart from carbon monoxide, these oxides are unimportant for A level chemistry purposes. They all disproportionate on heating - that is, one molecule undergoes both oxidation and reduction. For example, in the case of SiO, one molecule is reduced to silicon while the other is oxidised to silicon dioxide. They all undergo the change:

In the case of carbon monoxide, a catalyst is needed even at relatively high temperatures. These changes reflect the fact that the +4 oxidation state (in the dioxides) is more stable than the +2 state at the top of Group 4. SnO and PbO These are stable to heat.

The dioxides The dioxides are stable to heat except for PbO2. This decomposes on heating to give lead(II) oxide and oxygen.

This reflects the greater stability of the +2 oxidation state at the bottom of Group 4. Pb3O4 (thought of as 2PbO.PbO2) will, of course, also give off oxygen on heating to give simple PbO.

OXIDATION STATE TRENDS IN GROUP 4 This page explores the oxidation states (oxidation numbers) shown by the Group 4 elements - carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). It looks at the increasing tendency of the elements to form compounds in which their oxidation states are +2, particularly with reference to tin and lead. Note: If you aren't happy about oxidation and reduction (including the use of oxidation states), it is essential to follow this link before you go any further. Use the BACK button on your browser to return quickly to this page.

Some examples of the trends in oxidation states

The overall trend The typical oxidation state shown by elements in Group 4 is +4, found in compounds like CCl4, SiCl4 and SnO2.
Warning: Don't fall into the trap of quoting CH4 as an example of carbon with a typical oxidation state of +4. Because carbon is more electronegative than hydrogen, its oxidation state in this instance is -4!

However, as you go down the Group, there are more and more examples where the oxidation state is +2, such as SnCl2, PbO, and Pb2+. With tin, the +4 state is still more stable than the +2, but by the time you get to lead, the +2 state is the more stable - and dominates the chemistry of lead.

An example from carbon chemistry The only common example of the +2 oxidation state in carbon chemistry occurs in carbon monoxide, CO. Carbon monoxide is a strong reducing agent because it is easily oxidised to carbon dioxide - where the oxidation state is the more thermodynamically stable +4. For example, carbon monoxide reduces many hot metal oxides to the metal - a reaction which is used, for example, in the extraction of iron in a blast furnace.

Examples from tin chemistry By the time you get down the Group as far as tin, the +2 state has become increasingly common, and there is a good range of both tin(II) and tin(IV) compounds. However, tin(IV) is still the more stable oxidation state of tin. That means that it will be fairly easy to convert tin(II) compounds into tin(IV) compounds. This is best shown in the fact that Sn2+ ions in solution are good reducing agents. For example, a solution containing tin(II) ions (for

example, tin(II) chloride solution) will reduce a solution of iodine to iodide ions. In the process, the tin(II) ions are oxidised to tin(IV) ions.

Note: For simplicity, I am writing this equation (and the next few) as if the product contained simple tin(IV) ions. In fact, simple tin(IV) ions don't exist in solution. In these examples, they will usually be a part of a much larger complex ion. Don't worry about this at this level.

Tin(II) ions also reduce iron(III) ions to iron(II) ions. For example, tin(II) chloride solution will reduce iron(III) chloride solution to iron(II) chloride solution. In the process, the tin(II) ions are oxidised to the more stable tin(IV) ions.

Tin(II) ions will also, of course, be easily oxidised by powerful oxidising agents like acidified potassium manganate(VII) solution (potassium permanganate solution). This reaction could be used as a titration to find the concentration of tin(II) ions in a solution.

Note: If you aren't happy about titration calculations (including those involving potassium manganate(VII) ), you might be interested in my chemistry calculations book.

And as a final example . . . In organic chemistry, tin and concentrated hydrochloric acid are traditionally used to reduce nitrobenzene to phenylamine (aniline). This reaction involves the tin first being oxidised to tin(II) ions and then further to the preferred tin(IV) ions.
Note: This reaction is dealt with in some detail in the organic chemistry section of the site on a page about the preparation of phenylamine. Use the BACK button on your browser to return to this page if you choose to follow this link.

Examples from lead chemistry With lead, the situation is reversed. This time, the lead(II) oxidation state is the more stable, and there is a strong tendency for lead(IV) compounds to react to give lead(II) compounds. Lead(IV) chloride, for example, decomposes at room temperature to give lead(II) chloride and chlorine gas:

. . . and lead(IV) oxide decomposes on heating to give lead(II) oxide and oxygen.

Lead(IV) oxide also reacts with concentrated hydrochloric acid, oxidising some of the chloride ions in the acid to chlorine gas. Once again, the lead is reduced from the +4 to the more stable +2 state.

Trying to explain the trends in oxidation states

There's nothing surprising about the normal Group oxidation state of +4. All of the elements in the group have the outer electronic structure ns2npx1npy1, where n varies from 2 (for carbon) to 6 (for lead). The oxidation state of +4 is where all these outer electrons are directly involved in

the bonding. As you get closer to the bottom of the Group, there is an increasing tendency for the s2 pair not to be used in the bonding. This is often known as the inert pair effect - and is dominant in lead chemistry. However, just giving it a name like "inert pair effect" explains nothing. You need to look at two different explanations depending on whether you are talking about the formation of ionic or covalent bonds.
Note: What follows is quite likely to be way beyond what you need for the purposes of UK A level (or its equivalent) - and is there mainly for interest. To be sure, refer to your syllabus and, more importantly, to past exam papers and mark schemes. If you are working towards a UKbased exam and haven't got these, follow this link to the syllabuses page to find out how to get hold of them.

The inert pair effect in the formation of ionic bonds If the elements in Group 4 form 2+ ions, they will lose the p electrons, leaving the s2 pair unused. For example, to form a lead(II) ion, lead will lose the two 6p electrons, but the 6s electrons will be left unchanged an "inert pair". You would normally expect ionisation energies to fall as

you go down a Group as the electrons get further from the nucleus. That doesn't quite happen in Group 4. This first chart shows how the total ionisation energy needed to form the 2+ ions varies as you go down the Group. The values are all in kJ mol-1.

Notice the slight increase between tin and lead. This means that it is slightly more difficult to remove the p electrons from lead than from tin. However, if you look at the pattern for the loss of all four electrons, the discrepancy between tin and lead is much more marked. The relatively large increase between tin and lead must be because the 6s2 pair is significantly more difficult to remove in lead than the corresponding 5s2 pair in tin.

Again, the values are all in kJ mol-1, and the two charts are to approximately the same scale. The reasons for all this lie in the Theory of Relativity. With the heavier elements like lead, there is what is known as a relativistic contraction of the electrons which tends to draw the electrons closer to the nucleus than you would expect. Because they are closer to the nucleus, they are more difficult to remove. The heavier the element, the greater this effect. This affects s electrons much more than p electrons. In the case of lead, the relativistic contraction makes it energetically more difficult to remove the 6s electrons than you might expect. The energy releasing terms when ions are formed (like lattice enthalpy or hydration enthalpy) obviously aren't enough to compensate for this extra energy. That means that it doesn't make energetic sense for lead to form 4+ ions.
Note: If you want to find out more about the relativistic

contraction, try a Google search on relativistic contraction electrons - but expect to get involved in some heavy reading!

The inert pair effect in the formation of covalent bonds You need to think about why carbon normally forms four covalent bonds rather than two. Using the electrons-in-boxes notation, the outer electronic structure of carbon looks like this:

There are only two unpaired electrons. Before carbon forms bonds, though, it normally promotes one of the s electrons to the empty p orbital.

That leaves 4 unpaired electrons which (after hybridisation) can go on to form 4 covalent bonds. It is worth supplying the energy to promote the s electron, because the carbon can then form twice as many covalent bonds. Each covalent bond that forms

releases energy, and this is more than enough to supply the energy needed for the promotion. One possible explanation for the reluctance of lead to do the same thing lies in falling bond energies as you go down the Group. Bond energies tend to fall as atoms get bigger and the bonding pair is further from the two nuclei and better screened from them. For example, the energy released when two extra Pb-X bonds (where X is H or Cl or whatever) are formed may no longer be enough to compensate for the extra energy needed to promote a 6s electron into the empty 6p orbital. This would would be made worse, of course, if the energy gap between the 6s and 6p orbitals was increased by the relativistic contraction of the 6s orbital.

Explanations in terms of E values You can only really apply this to reactions involving tin or lead ions. The only relevant E values quoted in the Data Booklet that you will have in an exam (and which you will find towards the end of the syllabus) are:

Remember that the E values give a measure of the position of the various equilibria. The more positive the E value, the further it lies to the right. You will see that the equilibria involving lead(IV) are further to the right than the one involving tin(IV). That means that the lead(IV) ions or compound are more likely to pick up electrons and go to the the lead(II) side.

Picking up electrons happens when a compound oxidises something else. That means that lead(IV) compounds are better oxidising agents than tin(IV) compounds. Why does this happen? Because for lead, the +2 oxidation state is more stable relative to the +4 state than tin(II) is to tin(IV).
Note: This doesn't, of course, actually explain anything! The reason for the relative stability of the lead(II) is extremely complicated. You don't need to worry about that. CIE couldn't ask this unless they had specifically mentioned it in the syllabus.

Let's look at a couple of examples of the sort you might be asked about in an exam. Why does lead(IV) oxide oxidise concentrated hydrochloric acid to chlorine? You may remember that if you treat lead(IV) oxide with very cold concentrated hydrochloric acid, you get some lead(IV) chloride formed. You may also remember that if you warm this, the lead(IV) chloride decomposes to give lead(II) chloride and chlorine. If you reacted lead(IV) oxide with hot concentrated hydrochloric acid, you could think about this in another way. The lead(IV) oxide is a strong enough oxidising agent to oxidise the hydrochloric acid to chlorine. Think about the E values:

Where you couple two of these equilibria together in a test tube, the more positive one moves to the right, and the less positive one moves to the left. In this case, starting from the chloride ions in the hydrochloric acid, and the lead(IV) oxide (and the hydrogen ions from the acid), the lead equilibrium moves to the right, and the chlorine one to the left.

Chlorine gas is formed, and a lead(II) compound.

Note: Taking your E revision a stage further: E values apply only when the ion concentrations are 1 -3 mol dm . In the case of concentrated hydrochloric acid, -3 they will be more like 10 mol dm . Increasing the concentration of something on one side of an equilibrium will move the position of equilibrium towards the other side. The effect of this is that the E value for the chlorine equilibrium will be less than the +1.36 value we are assuming, and the lead equilibrium value will be greater than the +1.47. There will therefore be even more difference between the positions of the two equilibria than the E values suggest, making the reaction even more likely.

The effect of tin or lead ions on the interconversion of iron(II) and iron(III) Look at these E values:

Iron(III) ions and tin(II) ions What would be the effect of mixing solutions containing tin(II) ions and iron(III) ions? Try to work this out before you read on. The iron has a greater tendency to move to the right than the tin one, because the E is more positive. That means that the iron(III) ions will gain electrons (be reduced) to iron(II) ions. The tin(II) ions will lose electrons (be oxidised) to tin(IV) ions. In other words, tin(II) ions are strong enough reducing agents to

reduce iron(III) ions to iron(II) ions. Iron(III) ions and lead(II) ions Now suppose you tried a similar thing by mixing solutions containing lead(II) ions and iron(III) ions. This time nothing could happen. The more positive E value belongs to the lead equilibrium. That one is the one that would have to move to the right. But if you start from lead(II) ions, it is already as far to the right as it can go. Any reaction would involve the equilibrium moving to the left - but that is impossible according to the E values. The more positive one has to move to the right; the less positive one to the left.

These statements are a brief introduction to ceramic materials. Before you go on, you should find and read the statements in your copy of the syllabus.

The IUPAC Gold Book defines ceramic as Rigid material that consists of an infinite three-dimensional network of sintered crystalline grains comprising metals bonded to carbon, nitrogen or oxygen. Note: The term ceramic generally applies to any class of inorganic, non-metallic product subjected to high temperature during manufacture or use. In the first sentence, the word "sintered" refers to the process of sintering. Sintering happens when you heat a powdered material to a temperature below its melting point, and new bonds are formed between the grains of powder to form one large mass.

The most commonly used definition (including by CIE) tends to include what the note says. There are several modern ceramic materials which don't actually involve a metal. The syllabus, for example, includes silicon(IV) oxide, and there is a past question which tells you that silicon carbide, SiC, is used in ceramics, and asks you to deduce things about it. This is such a huge topic that I will just stick closely to what the syllabus asks.

Statement 4(f) This deals with the properties of some ceramic materials, and talks about the physical properties of ceramics in terms of their structures. The structures I have a problem with this, because I disagree with the syllabus statement! This says ". . . in terms of their giant molecular structure". A giant molecular structure (I prefer the term giant covalent structure) consists of covalent bonds holding together huge numbers of atoms. If you have been working through previous statements in Section 4, you will already have read about these in learning outcome 4(e)(iii). The problem is that some of the ceramics mentioned in 4(g) aren't covalent. Magnesium oxide is ionic, and aluminium oxide is also mainly ionic. They do indeed have giant structures, but they have giant ionic structures. Other more complex ceramics will contain both ionic and covalent bonds, some of which may be highly polar. What is, however, true is that ceramics all have giant structures of one type or another, with strong bonds between the atoms (or ions) which make them up.

The physical properties Strength The strong bonds holding the atoms (or ions) together in three dimensions will make the ceramic hard and strong, but also brittle. Think about a ceramic wall or floor tile as a simple example. The tile is obviously hard, and you can stand on a floor tile, or place heavy furniture on it without it breaking - so it is strong. On the other hand, it isn't difficult to break a tile in half by snapping it, especially if you score a shallow line on it first with a cutting tool - it is brittle. This is unlike a metal, which would bend before it fractured - you can bend or stretch metals. Atoms in metals can roll over each other without breaking the bonds. In a ceramic, you either have to break covalent bonds in three dimensions or, if you distort an ionic lattice, it brings like charges together, which splits the lattice apart. The lattice is either all in one piece, or else broken apart. Melting points

Ceramics have high melting points because of the need to break the strong covalent or ionic bonds holding the giant structure together. It takes a very high temperature to do this. Electrical conductivity Most ceramics are good electrical insulators. If they are covalent, there are no free electrons to move around. If they are ionic, the ions aren't free to move in the solid. Examples of electrically conducting (including superconducting) ceramics are beyond the scope of this syllabus.

Statement 4(g) This deals with the uses of modern ceramic materials involving magnesium oxide, aluminium oxide and silicon(IV) oxide, and the relationship with their structures.

Magnesium oxide Ceramics made from magnesium oxide are used in (amongst other things):

furnace linings (refractory bricks), because the ceramic has a high melting point (strong forces in the giant structure); heating elements (for example for electric cookers), because the ceramic is good electrical insulator (no free electrons, and the ions aren't free to move in the solid). A heating element will often have a metal core which heats up when an electric current flows through it. For obvious safety reasons, this has to have an electrically insulating layer around it with a high melting point (typical ceramic properties), and a further metal layer on the outside to protect the brittle ceramic.

Aluminium oxide Various web sources describe this as the most important oxide ceramic. Uses of aluminium oxide ceramics include:

high temperature and high voltage electrical insulators, because the ceramic has a high melting point and is a good electrical insulator (strong attractions in the giant structure; no free electrons, and the ions aren't free to move either);

replacement hip joints. Hip joints are a ball and socket arrangement, and the ball or socket can both be made of aluminium oxide ceramic material. The strong forces holding the aluminium and oxide ions together make it very resistant to wear. Aluminium oxide is also chemically resistant because of the large amount of energy needed to separate the ions. The photograph (taken from Wikipedia) shows an artificial hip joint in pieces. This one has a ceramic ball, but a polythene cup.

Silicon(IV) oxide (silicon dioxide) Uses of silicon dioxide ceramics include:

as furnace linings (refractory bricks) in furnaces for the production of glass, because the giant covalent structure has a very high melting point due to the strength of the Si-O covalent bonds in three dimensions; to make ceramic tiles to protect the space shuttle. The tiles are light, and have a high melting point.

You will notice that I haven't specifically quoted two of the uses suggested in the syllabus - the use in glass and crockery. The reason is that although silicon(IV) oxide, for example, is used to make glass, the resulting glass isn't pure silicon(IV) oxide. Instead, it will be a complex lattice with (mainly) ionic bonds to various other metal ions present.

This diagram (also taken from Wikipedia) shows a possible structure for a particular glass.

To describe this as silicon(IV) oxide would be chemical nonsense! It is possible to make a ceramic containing pure silicon(IV) oxide which looks like glass, but it isn't normal glass. The only times I ever came across it were in a chemistry lab.

The problem with pottery is even worse. Various kinds of pottery are made by heating to high temperatures various clays or mixtures of clay with other things. The results are chemically very complex. It would be completely misleading to describe pottery as being made of any of the ceramic materials mentioned in this syllabus statement. Glass There are various sorts of glass, but the essential process is heating together sodium carbonate with sand. The sand will contain mainly silicon dioxide (silica) and other minerals. If you have looked at the link above, you will know that glass is a complex structure. Glass manufacturers give compositions in forms like:

"Most commercial glasses have roughly similar chemical compositions of: 70% - 74% SiO2 (silica) 12% - 16% Na2O (sodium oxide) 5% - 11% CaO (calcium oxide) 1% - 3% MgO (magnesium oxide) 1% - 3% Al2O3 (aluminium oxide)" (quoted from the British Glass website) It doesn't mean that the glass is really a mixture of these substances. It simply has a complex structure made up of elements like Si, Na, Ca, Mg, Al and oxygen, in the way shown in the diagram on the link above. The teacher support material also mentions Pyrex. You will have come across this in the lab in the form of various glassware. It has a higher melting point than ordinary glass, and can stand rapid changes of temperature better. Pyrex is a particular brand of borosilicate glass - containing boron as well as silicon.

Pottery and china These are made from various clays which contain minerals known as aluminosilicates. Baking these sets up cross-links which make the products hard and high melting.

A final comment Don't spend too much time on this. It would be asked in Paper 4, and there is so much important chemistry that has to be tested in that paper, that it is hard to imagine the examiners wasting many marks on this kind of thing - and even that would only happen very infrequently. In the 8 exam sessions up to November 2010, the only question I can find on this said: "What are the properties of a ceramic material? Why is silicon(IV) oxide very suitable as a component of ceramics?" It was worth 2 marks. For the first mark, they wanted at least two of: hard, high melting point, electrical insulator. Those are typical of any ceramic material, of course.

For the second mark, all they wanted was the fact that silicon dioxide has strong covalent bonds.